Curing for polyallophanate compositions through undercoat acid neutralization

ABSTRACT

The present invention provides a system comprising an allophanate composition comprising a neutralized polyol, a polyuretdione resin, a tertiary amine catalyst, an additive package, and a reducer and a neutralized basecoat comprising an acid scavenger and a pigment. The resulting allophanate system may be used to make coatings, adhesives, castings, composites, and sealants in which clear-coating on neutralized pigmented basecoats is much improved in comparison to non-neutralized basecoats.

FIELD OF THE INVENTION

The present invention relates, in general to polymers, and morespecifically, to polymers made with neutralized polyols, uretdiones andtertiary amine catalysts that cure over neutralized basecoats. Theresulting allophanate polymers may be used to make coatings, adhesives,castings, composites, and sealants.

BACKGROUND OF THE INVENTION

Polyurethane-forming compositions are widely used in a variety ofcommercial, industrial and household applications, such as in automotiveclear-coat and seat cushion applications. Polyurethane systems thatemploy isocyanates which are pre-reacted with monofunctional reagents toform relatively thermally labile compounds are called blockedisocyanates. Uretdiones are a type of blocked isocyanate. Uretdiones aretypically prepared by dimerizing an isocyanate to form uretdione(s) withunreacted isocyanate end-groups which can then be extended with a polyolto form a polymeric material containing two or more uretdione groups inthe polymer chain. In some literature, uretdiones are referred to as“1,3-diaza-2,4-cyclobutanones”, “1,3-diazatidin-2,4-diones”,“2,4-dioxo-1,3-diazetidines”, “urethdiones” or “uretidiones”. Typically,the polymer has few, if any, free isocyanate groups, which is achievedby controlling the stoichiometry of the polyisocyanate, of the polyol,and by the use of a blocking agent.

The reaction of uretdiones with polyols to form polyurethane coatings iswell known in the art, especially in polyurethane powder coatings.However, the creation of allophanates from uretdiones and polyols atambient or low temperatures in the presence of a tertiary amine catalysthas not been well-studied in the literature. To the best of the presentinventors' knowledge, no one has developed a cross-linking approachusing neutralized polyols to promote successful conversion of uretdioneto allophanate at ambient or low temperatures in the presence oftertiary amine catalysts over neutralized basecoats.

SUMMARY OF THE INVENTION

Uretdione-based clear coats face some challenges when applied overpigmented basecoats due to the acidic nature of the basecoats. Whenbasecoats are neutralized with epoxy or carbodiimide, uretdione-basedclear-coating is much improved in comparison to non-neutralizedbasecoats.

Accordingly, the present invention attempts to alleviate problemsinherent in the art by providing such an alternative cross-linkingapproach to obtain compositions having physical properties similar tothose of polyurethane compositions. To increase the conversion rate ofuretdione and polyol to form allophanate groups at ambient or lowtemperatures in the presence of a tertiary amine catalyst over aneutralized basecoat, the acidity of the polyol, and basecoat, and moregenerally, the acidity of the system is minimized or eliminated. Thus,various embodiments of the inventive approach involve crosslinkingpolyuretdione resins with neutralized polyols in the presence of atertiary amine catalyst over a neutralized basecoat. The polyol may beneutralized by reaction with an epoxy or a carbodiimide at a temperatureranging from room temperature (21° C.-24° C.) to 120° C. The resultingallophanate polymer may be used to make coatings, adhesives, castings,composites, and sealants. The basecoat may be neutralized by reactionwith an epoxy or a carbodiimide. The uretdione-based clear-coating maybe applied over basecoats.

It is understood that the invention disclosed and described in thisspecification is not limited to the embodiments summarized in thisSummary.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will now be described for purposes of illustrationand not limitation. Except in the operating examples, or where otherwiseindicated, all numbers expressing quantities, percentages, and so forthin the specification are to be understood as being modified in allinstances by the term “about.”

Any numerical range recited in this specification is intended to includeall sub-ranges of the same numerical precision subsumed within therecited range. For example, a range of “1.0 to 10.0” is intended toinclude all sub-ranges between (and including) the recited minimum valueof 1.0 and the recited maximum value of 10.0, that is, having a minimumvalue equal to or greater than 1.0 and a maximum value equal to or lessthan 10.0, such as, for example, 2.4 to 7.6. Any maximum numericallimitation recited in this specification is intended to include alllower numerical limitations subsumed therein and any minimum numericallimitation recited in this specification is intended to include allhigher numerical limitations subsumed therein. Accordingly, Applicantsreserve the right to amend this specification, including the claims, toexpressly recite any sub-range subsumed within the ranges expresslyrecited herein. All such ranges are intended to be inherently describedin this specification such that amending to expressly recite any suchsub-ranges would comply with the requirements of 35 U.S.C. § 112(a), and35 U.S.C. § 132(a).

Any patent, publication, or other disclosure material identified hereinis incorporated by reference into this specification in its entiretyunless otherwise indicated, but only to the extent that the incorporatedmaterial does not conflict with existing definitions, statements, orother disclosure material expressly set forth in this specification. Assuch, and to the extent necessary, the express disclosure as set forthin this specification supersedes any conflicting material incorporatedby reference herein. Any material, or portion thereof, that is said tobe incorporated by reference into this specification, but whichconflicts with existing definitions, statements, or other disclosurematerial set forth herein, is only incorporated to the extent that noconflict arises between that incorporated material and the existingdisclosure material. Applicants reserve the right to amend thisspecification to expressly recite any subject matter, or portionthereof, incorporated by reference herein.

Reference throughout this specification to “various non-limitingembodiments,” “certain embodiments,” or the like, means that aparticular feature or characteristic may be included in an embodiment.Thus, use of the phrase “in various non-limiting embodiments,” “incertain embodiments,” or the like, in this specification does notnecessarily refer to a common embodiment, and may refer to differentembodiments. Further, the particular features or characteristics may becombined in any suitable manner in one or more embodiments. Thus, theparticular features or characteristics illustrated or described inconnection with various or certain embodiments may be combined, in wholeor in part, with the features or characteristics of one or more otherembodiments without limitation. Such modifications and variations areintended to be included within the scope of the present specification.

The grammatical articles “a”, “an”, and “the”, as used herein, areintended to include “at least one” or “one or more”, unless otherwiseindicated, even if “at least one” or “one or more” is expressly used incertain instances. Thus, these articles are used in this specificationto refer to one or more than one (i.e., to “at least one”) of thegrammatical objects of the article. By way of example, and withoutlimitation, “a component” means one or more components, and thus,possibly, more than one component is contemplated and may be employed orused in an implementation of the described embodiments. Further, the useof a singular noun includes the plural, and the use of a plural nounincludes the singular, unless the context of the usage requiresotherwise.

In various embodiments, the present invention provides a reactionmixture comprising a polyuretdione resin; a neutralized polyol and atertiary amine catalyst; and optionally, an additive package (e.g. flowcontrol, wetting agent), pigment (colorant), and solvent applied overneutralized basecoats. In certain embodiments, the present inventionfurther provides a method of making an allophanate polymer comprisingreacting a polyuretdione resin with a neutralized polyol in the presenceof a tertiary amine catalyst, wherein the reaction mixture optionallyincludes an additive package (e.g., flow control, wetting agent), apigment (colorant), and solvent applied over neutralized basecoats. Thepolyol and the basecoat may be neutralized by reaction with acarbodiimide or an epoxy acid scavenger at a temperature ranging fromroom temperature (21° C. -24° C.) to 120° C. Thus, the present inventionprovides a method for producing an allophanate polymer over neutralizedbasecoats by the following route:

The uretdione based clear-coating may be applied over basecoats. Theinventive allophanate polymer system is particularly applicable inproducing coatings, adhesives, castings, composites, and sealants.

As used herein, the term “polymer” encompasses prepolymers, oligomersand both homopolymers and copolymers; the prefix “poly” in this contextreferring to two or more. As used herein, the term “molecular weight”,when used in reference to a polymer, refers to the number averagemolecular weight, unless otherwise specified.

As used herein, the term “polyol” refers to compounds comprising atleast two free hydroxy groups. Polyols include polymers comprisingpendant and terminal hydroxy groups.

As used herein, the term “coating composition” refers to a mixture ofchemical components that will cure and form a coating when applied to asubstrate.

The terms “adhesive” or “adhesive compound”, refer to any substance thatcan adhere or bond two items together. Implicit in the definition of an“adhesive composition” or “adhesive formulation” is the concept that thecomposition or formulation is a combination or mixture of more than onespecies, component or compound, which can include adhesive monomers,oligomers, and polymers along with other materials.

A “sealant composition” refers to a composition which may be applied toone or more surfaces to form a protective barrier, for example toprevent ingress or egress of solid, liquid or gaseous material oralternatively to allow selective permeability through the barrier to gasand liquid. In particular, it may provide a seal between surfaces.

A “casting composition” refers to a mixture of liquid chemicalcomponents which is usually poured into a mold containing a hollowcavity of the desired shape, and then allowed to solidify.

A “composite” refers to a material made from two or more polymers,optionally containing other kinds of materials. A composite hasdifferent properties from those of the individual polymers/materialswhich make it up.

“Cured,” “cured composition” or “cured compound” refers to componentsand mixtures obtained from reactive curable original compound(s) ormixture(s) thereof which have undergone chemical and/or physical changessuch that the original compound(s) or mixture(s) is(are) transformedinto a solid, substantially non-flowing material. A typical curingprocess may involve crosslinking.

The term “curable” means that an original compound(s) or compositionmaterial(s) can be transformed into a solid, substantially non-flowingmaterial by means of chemical reaction, crosslinking, radiationcrosslinking, or the like. Thus, compositions of the invention arecurable, but unless otherwise specified, the original compound(s) orcomposition material(s) is(are) not cured.

The term “basecoat” means the first (undermost) layer applied to thesurface of a substrate prior to application of a subsequent or finishingcoat. The term encompasses basecoats, undercoats, and tiecoats.

The components useful in the present invention comprise apolyisocyanate. As used herein, the term “polyisocyanate” refers tocompounds comprising at least two unreacted isocyanate groups, such asthree or more unreacted isocyanate groups. The polyisocyanate maycomprise diisocyanates such as linear aliphatic polyisocyanates,aromatic polyisocyanates, cycloaliphatic polyisocyanates and aralkylpolyisocyanates.

Particularly preferred in the present invention are those blockedisocyanates known as uretdiones. The uretdiones useful in the inventionmay be obtained by catalytic dimerization of polyisocyanates by methodswhich are known to those skilled in the art. Examples of dimerizationcatalysts include, but are not limited to, trialkylphosphines,aminophosphines and aminopyradines such as dimethylaminopyridines, andtris(dimethylamino)phosphine, as well as any other dimerizationcatalyst. The result of the dimerization reaction depends, in a mannerknown to the skilled person, on the catalyst used, on the processconditions and on the polyisocyanates employed. In particular, it ispossible for products to be formed which contain on average more thanone uretdione group per molecule, the number of uretdione groups beingsubject to a distribution. The (poly)uretdiones may optionally containisocyanurate, biuret, allophanate, and iminooxadiazine dione groups inaddition to the uretdione groups.

The uretdiones are NCO-functional compounds and may be subjected to afurther reaction, for example, blocking of the free NCO groups orfurther reaction of NCO groups with NCO-reactive compounds having afunctionality of two or more to extend the uretdiones to formpolyuretdione prepolymers. This gives compounds containing uretdionegroups and of higher molecular weight, which, depending on the chosenproportions, may also contain NCO groups, be free of NCO groups or maycontain isocyanate groups that are blocked.

Suitable blocking agents include, but are not limited to, alcohols,lactams, oximes, malonates, alkyl acetoacetates, triazoles, phenols,imidazoles, pyrazoles and amines, such as butanone oxime,diisopropylamine, 1,2,4-triazole, dimethyl-1,2,4-triazole, imidazole,diethyl malonate, ethyl acetoacetate, acetone oxime,3,5-dimethylpyrazole, caprolactam, N-tert-butylbenzylamine andcyclopentanone including mixtures of these blocking agents.

Examples of NCO-reactive compounds with a functionality of two or moreinclude polyols. In some embodiments, the NCO-reactive compounds areused in amounts sufficient to react with all free NCO groups in theuretdione. By “free NCO groups” it is meant all NCO groups not presentas part of the uretdione, isocyanurate, biuret, allophanate andiminooxadiazine dione groups.

The resulting polyuretdione contains at least 2, such as from 2 to 10uretdione groups. More preferably, the polyuretdione contains from 5% to45% uretdione, 10% to 55% urethane, and less than 2% isocyanate groups.The percentages are by weight based on total weight of resin containinguretdione, urethane, and isocyanate.

Suitable polyisocyanates for producing the uretdiones useful inembodiments of the invention include, organic diisocyanates representedby the formula

R(NCO)₂

wherein R represents an organic group obtained by removing theisocyanate groups from an organic diisocyanate having(cyclo)aliphatically bound isocyanate groups and a molecular weight of112 to 1000, preferably 140 to 400. Preferred diisocyanates for theinvention are those represented by the formula wherein R represents adivalent aliphatic hydrocarbon group having from 4 to 18 carbon atoms, adivalent cycloaliphatic hydrocarbon group having from 5 to 15 carbonatoms, or a divalent araliphatic hydrocarbon group having from 7 to 15carbon atoms.

Examples of the organic diisocyanates which are particularly suitablefor the present invention include 1,4-tetramethylene diisocyanate,1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylenediisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and1,4-diisocyanate, 1-isocyanato-2-isocyanato-methyl cyclopentane,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane (isophoronediisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 1,3- and1,4-bis(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,α,α,α′,α′-tetramethyl-1,3- and 1,4-xylene diisocyanate,1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, and 2,4- and2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI),diphenylmethane diisocyanate (MDI), pentane diisocyanate(PDI)—bio-based, and, isomers of any of these; or combinations of any ofthese. Mixtures of diisocyanates may also be used. Preferreddiisocyanates include 1,6-hexamethylene diisocyanate, isophoronediisocyanate, and bis(4-isocyanatocyclohexyl)-methane because they arereadily available and yield relatively low viscosity polyuretdionepolyurethane oligomers.

In some embodiments, the uretdiones may comprise from 35% to 85% resinsolids in the composition of present invention, excluding solvents,additives or pigments (colorants). In other embodiments, from 50% to 85%and in still other embodiments, 60% to 85%. The uretdiones may compriseany resin solids amount ranging between any combinations of thesevalues, inclusive of the recited values.

In various embodiments of the present invention, the reaction mixturecontaining the polyuretdione and the neutralized polyol in the presenceof a tertiary amine catalyst may be heated to a temperature of 140° C.,in other embodiments to a temperature of from 20° C. to 140° C.

The polyols useful in the present invention may be either low molecularweight (62-399 Da, as determined by gel permeation chromatography) orhigh molecular weight (400 to 10,000 Da, as determined by gel permeationchromatography) materials and in various embodiments will have averagehydroxyl values as determined by ASTM E222-10, Method B, of between 1000and 10, and preferably between 500 and 50.

The polyols in the present invention include low molecular weight diols,triols and higher alcohols and polymeric polyols such as polyesterpolyols, polyether polyols, polycarbonate polyols, polyurethane polyolsand hydroxy-containing (meth)acrylic polymers.

The low molecular weight diols, triols and higher alcohols useful in theinstant invention are known to those skilled in the art. In manyembodiments, they are monomeric and have hydroxy values of 200 andabove, usually within the range of 1500 to 200. Such materials includealiphatic polyols, particularly alkylene polyols containing from 2 to 18carbon atoms. Examples include ethylene glycol, 1,4-butanediol,1,6-hexanediol; cycloaliphatic polyols such as cyclohexane dimethanol.Examples of triols and higher alcohols include trimethylol propane andpentaerythritol. Also useful are polyols containing ether linkages suchas diethylene glycol and triethylene glycol.

In various embodiments, the suitable polyols are polymeric polyolshaving hydroxyl values less than 200, such as 10 to 180. Examples ofpolymeric polyols include polyalkylene ether polyols, polyester polyolsincluding hydroxyl-containing polycaprolactones, hydroxy-containing(meth)acrylic polymers, polycarbonate polyols and polyurethane polymers.

Examples of polyether polyols include poly(oxytetramethylene) glycols,poly(oxyethylene) glycols, and the reaction product of ethylene glycolwith a mixture of propylene oxide and ethylene oxide.

Also useful are polyether polyols formed from the oxyalkylation ofvarious polyols, for example, glycols such as ethylene glycol,1,4-butane glycol, 1,6-hexanediol, and the like, or higher polyols, suchas trimethylol propane, pentaerythritol and the like. One commonlyutilized oxyalkylation method is by reacting a polyol with an alkyleneoxide, for example, ethylene oxide in the presence of an acidic or basiccatalyst.

Polyester polyols can also be used as a polymeric polyol component inthe certain embodiments of the invention. The polyester polyols can beprepared by the polyesterification of organic polycarboxylic acids oranhydrides thereof with organic polyols. Preferably, the polycarboxylicacids and polyols are aliphatic or aromatic dibasic acids and diols.

The diols which may be employed in making the polyester include alkyleneglycols, such as ethylene glycol and butylene glycol, neopentyl glycoland other glycols such as cyclohexane dimethanol, caprolactone diol (forexample, the reaction product of caprolactone and ethylene glycol),polyether glycols, for example, poly(oxytetramethylene) glycol and thelike. However, other diols of various types and, as indicated, polyolsof higher functionality may also be utilized in various embodiments ofthe invention. Such higher polyols can include, for example, trimethylolpropane, trimethylol ethane, pentaerythritol, and the like, as well ashigher molecular weight polyols such as those produced by oxyalkylatinglow molecular weight polyols. An example of such high molecular weightpolyol is the reaction product of 20 moles of ethylene oxide per mole oftrimethylol propane.

The acid component of the polyester consists primarily of monomericcarboxylic acids or anhydrides having 2 to 18 carbon atoms per molecule.Among the acids which are useful are phthalic acid, isophthalic acid,terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid,adipic acid, azelaic acid, sebacic acid, maleic acid, glutaric acid,chlorendic acid, tetrachlorophthalic acid and other dicarboxylic acidsof varying types. Also, there may be employed higher polycarboxylicacids such as trimellitic acid and tricarballylic acid (where acids arereferred to above, it is understood that the anhydrides of those acidswhich form anhydrides can be used in place of the acid). Also, loweralkyl esters of acids such as dimethyl glutamate can be used.

In addition to polyester polyols formed from polybasic acids andpolyols, polycaprolactone-type polyesters can also be employed. Theseproducts are formed from the reaction of a cyclic lactone such asε-caprolactone with a polyol with primary hydroxyls such as thosementioned above. Such products are described in U.S. Pat. No. 3,169,949.

In addition to the polyether and polyester polyols, hydroxy-containing(meth)acrylic polymers or (meth)acrylic polyols can be used as thepolyol component.

Among the (meth)acrylic polymers are polymers of 2 to 20 percent byweight primary hydroxy-containing vinyl monomers such as hydroxyalkylacrylate and methacrylate having 2 to 6 carbon atoms in the alkyl groupand 80 to 98 percent by weight of other ethylenically unsaturatedcopolymerizable materials such as alkyl(meth)acrylates; the percentagesby weight being based on the total weight of the monomeric charge.

Examples of suitable hydroxy alkyl(meth)acrylates are hydroxy ethyl andhydroxy butyl(meth)acrylate. Examples of suitable alkyl acrylates and(meth)acrylates are lauryl methacrylate, 2-ethylhexyl methacrylate andn-butyl acrylate.

In addition to the acrylates and methacrylates, other copolymerizablemonomers which can be copolymerized with the hydroxyalkyl(meth)acrylates include ethylenically unsaturated materials such asmonoolefinic and diolefinic hydrocarbons, halogenated monoolefinic anddiolefinic hydrocarbons, unsaturated esters of organic and inorganicacids, amides and esters of unsaturated acids, nitriles and unsaturatedacids and the like. Examples of such monomers include styrene,1,3-butadiene, acrylamide, acrylonitrile, α-methyl styrene, α-methylchlorostyrene, vinyl butyrate, vinyl acetate, alkyl chloride, divinylbenzene, diallyl itaconate, triallyl cyanurate and mixtures thereof.Preferably, these other ethylenically unsaturated materials are used inadmixture with the above-mentioned acrylates and methacrylates.

In certain embodiments of the invention, the polyol may be apolyurethane polyol. These polyols can be prepared by reacting any ofthe above-mentioned polyols with a minor amount of polyisocyanate(OH/NCO equivalent ratio greater than 1:1) so that free primary hydroxylgroups are present in the product. In addition to the high molecularweight polyols mentioned above, mixtures of both high molecular weightand low molecular weight polyols such as those mentioned above may beused.

Suitable hydroxy-functional polycarbonate polyols may be those preparedby reacting monomeric diols (such as 1,4-butanediol, 1,6-hexanediol,di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol,3-methyl-1,5-pentanediol, 4,4′-dimethylolcyclohexane and mixturesthereof) with diaryl carbonates (such as diphenyl carbonate, dialkylcarbonates (such as dimethyl carbonate and diethyl carbonate), alkylenecarbonates (such as ethylene carbonate or propylene carbonate), orphosgene. Optionally, a minor amount of higher functional, monomericpolyols, such as trimethylolpropane, glycerol or pentaerythritol, may beused.

In various embodiments of the invention, one or more of the polyol andthe basecoat is neutralized, for example by the addition of an epoxy ora carbodiimide acid scavenger. Acid scavengers should be covalentlybonded to the acidic groups within the polyol and within the basecoat,respectively. The present inventors believe, without wishing to be boundto any specific theory, that these acid scavengers covalently bind tocarboxylic and acrylic acid groups within the polyols or the basecoat.Such compounds are commercially available from a variety of supplierssuch as, for example, the monomeric carbodiimides sold under theSTABAXOL trade name from Rhein Chemie, and Bis(2,6-diisopropylphenyl)carbodiimide sold as EUSTAB HS-700 by Eutec Chemical Co., Ltd. Glycidylethers, such as 1,4-cyclohexanedimethanol diglycidyl ether, commerciallyavailable from Air Products as EPODIL 757 are also suitable in thepractice of the present invention.

In various embodiments, the neutralization of the polyol and of thebasecoat is conducted at any temperature ranging from room temperature(21° C.-24° C.) to 120° C., in other embodiments from room temperature(21° C.-24° C.) to 80° C. and in certain embodiments at room temperature(21° C.-24° C.).

Examples of suitable solvents include, but are not limited to aliphaticand aromatic hydrocarbons such as toluene, xylene, isooctane, acetone,butanone, methyl ethyl ketone, methyl amyl ketone, methyl isobutylketone, ethyl acetate, butyl acetate, pentyl acetate, tetrahydrofuran,ethyl ethoxypropionate, N-methyl-pyrrolidone, dimethylacetamide anddimethylformamide solvent naphtha, SOLVESSO 100 or HYDROSOL (ARAL),ethers, or mixtures thereof.

Urethane reducers are available in slow, medium and fast formulations,and may improve atomization, flow and leveling, which provide a smoothfinish with less “orange peel.” Depending on the “speed” of the reducer,it may contain various combinations of compounds including, but notlimited to, n-butyl acetate, ethyl acetate, 2-methoxy-1-methylethylacetate, 1-methoxy-2-propyl acetate, 2-methoxy-1-propyl acetate,2-ethoxyethyl acetate, n-heptane, methylcyclohexane, toluene, acetone,Varnish Makers and Painter (VM&P) naphtha, naphtha, light aliphaticsolvent naphtha, acetate, isobutyl acetate, mixed xylenes, ethylbenzene,methyl ethyl ketone, dimethyl ketone, methyl n-amyl ketone, methylisobutyl ketone, 1,2,4 trimethyl benzene, isopropylbenzene, ethylbenzene, 1-chloro-4 (triflouromethyl) benzene, propylene glycol methylether, and ethyl-3-ethoxy propionate.

In various embodiments, the basecoats useful in the invention includeone or more colorants, such as pigments and dyes. Any suitable pigmentcan be used in the basecoat of the present invention. Examples ofsuitable pigments include inorganic white pigments, inorganic chromaticpigments, iron oxide pigments, oxidic mixed-phase pigments, organicpigments, and inorganic black pigments.

As inorganic white pigments, mention should be made in particular ofoxides, such as titanium dioxide, zinc oxide (ZnO, zinc white),zirconium oxide, carbonates such as lead white, sulfates, such as leadsulfate, and sulfides such as zinc sulfide, and lithopones; titaniumdioxide is particularly preferred.

As inorganic chromatic pigments, mention should be made of those fromthe group of oxides and hydroxides in the form of their individualinorganic compounds or mixed phases, especially iron oxide pigments,chromium oxide pigments and oxidic mixed-phase pigments with rutile orspinel structure, and also bismuth vanadate, cadmium, cerium sulfide,chromate, ultramarine and iron blue pigments.

Examples of iron oxide pigments are Color Index Pigment Yellow 42,Pigment Red 101, Pigment Blue 11, Pigment Brown 6, and transparent ironoxide pigments. Examples of chromium oxide pigments are Color IndexPigment Green 17 and Pigment Green 18.

Examples of oxidic mixed-phase pigments are nickel titanium yellow andchromium titanium yellow, cobalt green and cobalt blue, zinc iron brownand chromium iron brown, and also iron manganese black and spinel black.

Examples of preferred organic pigments are those of the monoazo, disazo,laked azo, β-naphthol, Naphiol AS, benzimidazolone, disazo condensation,azo metal complex, isoindoline and isoindolinone series, and alsopolycyclic pigments such as those from the phthalocyanine, quinacridone,perylene, perinone, thioindigo, anthraquinone, dioxazine, quinophthaloneand diketopyrrolopyrrole series. Also suitable are laked dyes such asCa, Mg and Al lakes of dyes containing sulfonic acid or carboxylic acidgroups, and also carbon blacks, which for the purposes of thisspecification are taken to be pigments and of which a large number areknown. Mention should be made in particular of acidic to alkaline carbonblacks obtained by the furnace black process, and also chemicallysurface-modified carbon blacks, examples being sulfo- orcarboxyl-containing carbon blacks.

Examples of inorganic black pigments that should be mentioned includethose as already described above together with the inorganic chromaticpigments, especially black iron oxide, spinel black, and black oxidicmixed-phase pigments.

The basecoat can contain the pigment at a level of at least 1%, in somecases at least 2%, in other cases at least 5% by weight, in somesituations at least 10% and in other situations at least 15% by weight.Also, the basecoat can contain the pigment at a level of up to 60%, insome cases up to 50%, in other cases up to 40%, in some situations up to35% and in other situations up to 30% by weight, based on the weight ofbasecoat. The amount of the pigment in the basecoat can be any of thevalues recited above or can range between any of the values recitedabove.

The compositions of the present invention may further include any of avariety of additives such as defoamers, devolatilizers, surfactants,thickeners, flow control additives, pigments (colorants), or surfaceadditives.

The composition of the invention may be contacted with the basecoat byany methods known to those skilled in the art, including but not limitedto, spraying, dipping, flow coating, rolling, brushing, pouring, and thelike. In certain embodiments, the inventive compositions may be appliedin the form of paints or lacquers onto any compatible substrate, suchas, for example, metals, plastics, ceramics, glass, and naturalmaterials. In various embodiments, the composition of the invention isapplied as a single layer. In other embodiments, the inventivecomposition may be applied as multiple layers as needed.

The compositions of the present invention (clear-coating, top-coat, andbasecoat) may further include any of a variety of additives such asdefoamers, devolatilizers, surfactants, thickeners, flow controladditives, colorants (including pigments and dyes) or surface additives.

The composition of the invention may be contacted with a substrate byany methods known to those skilled in the art, including but not limitedto, spraying, dipping, flow coating, rolling, brushing, pouring, and thelike. In some embodiments, the inventive compositions may be applied inthe form of paints or lacquers onto any compatible substrate, such as,for example, metals, plastics, ceramics, glass, and natural materials.In certain embodiments, the inventive composition is applied as a singlelayer. In other embodiments, the composition of the present inventionmay be applied as multiple layers as needed.

EXAMPLES

The non-limiting and non-exhaustive examples that follow are intended tofurther describe various non-limiting and non-exhaustive embodimentswithout restricting the scope of the embodiments described in thisspecification. All quantities given in “parts” and “percents” areunderstood to be by weight, unless otherwise indicated. Although thepresent invention is described in the instant Examples in the context ofa coating, those skilled in the art will appreciate it can also beequally applicable to adhesives, castings, composites, and sealants.

The following materials were used in preparing the compositions of theExamples:

BASECOAT A a black polyester refinish basecoat, commercially availablefrom BASF under DIAMONT product line; BASECOAT B a white polyesterrefinish basecoat, commercially available from BASF under DIAMONTproduct line; REDUCER A a universal medium reducer, commerciallyavailable from BASF as RM UR 50, recommended for use in temperaturesbetween approximately 70° F.-85° F. (21.1° C.-29.4° C.); POLYOL A anaromatic free, branched hydroxyl-bearing polyester polyol, commerciallyavailable from Covestro as DESMOPHEN 775 XP; ADDITIVE A a monomericcarbodiimide, being used here as an acid scavenger for acidic groupswithin the polyols, commercially available from Rhein Chemie as STABAXOLI; ADDITIVE B epoxy reactive diluent, being used here as an acidscavenger for acidic groups within the polyols, commercially availablefrom Air Products as EPODIL 757. ADDITIVE C a surface additive onpolyacrylate-basis for solvent-borne coating systems and printing inks,commercially available from BYK Chemie as BYK 358N; CATALYST A1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), tertiary amine catalyst,commercially available from Air Products as POLYCAT DBU; URETDIONE A a1-isocyanato-3-isocyanatomethyl-3,5,5- trimethyl cyclohexane (isophoronediisocyanate or IPDI)-based uretdione prepolymer, proprietary product ofCovestro LLC, having a uretdione equivalent weight of 1,276 and aviscosity of 817 cPs in 50% butyl acetate (BA).

The basecoat formulations B, and C in Table I were prepared followingthe same procedure. In a 200 mL plastic container 100 mL of respectiveBASECOAT and 50 mL of REDUCER A were added. The resulting mixture wasmixed using a FLACKTEK speed mixer for one minute followed byapplication using a conventional HVLP spray.

The basecoat formulations D, E, F, and G in Table I were preparedfollowing the same procedure. ADDITVE A and ADDITIVE B had been mixedwith respective BASECOAT five weeks prior to application. In a 200 mLplastic container, 100 mL of respective BASECOAT and 3 parts respectiveADDITIVE mixture was mixed with 50 mL of REDUCER A. The resultingmixture was mixed using a FLACKTEK speed mixer for one minute followedby application using a conventional HVLP spray.

The clear-coat Formulations A, B, C, D, E, F, and G in Table I wereprepared as follows. POLYOL A had been reacted with ADDITIVE A prior toformulation. In a 200 mL plastic container 9.52 parts of the POLYOL Aand ADDITIVE A reaction mixture, 0.38 parts ADDITIVE C, 0.20 partsCATALYST A, 25.17 parts n-butyl acetate (n-BA), and 64.74 partsURETDIONE A were added. The resulting mixture was mixed using a FLACKTEKspeed mixer for one minute followed by application using a conventionalHVLP spray.

Zinc phosphate treated ACT B952, 4″×12″ (10.2 cm×30.5 cm) test panelswere used. Thickness of basecoat was 2 mils (50 μm) wet and thickness ofthe clear-coating was 5 mils (125 μm) wet (2 mils (50 μm) dry). Theresulting panels were used to test for MEK double rubs.

Films were cured at room temperature (21° C.-24° C.) for one day and forone week before testing.

MEK double rubs were measured according to ASTM D4752-10(2015). Resultsreported are an average of three readings for each formulation.

As can be appreciated by reference to Table I, Examples B through Ereceived the same clear-coat over basecoats that had been modified.Example A was a positive control that did not have a basecoat (metalpanel only). Examples B, and C were negative controls that hadnon-neutralized black and white basecoats respectively. Examples D, E,F, and G contained additives to neutralize acidic groups within thebasecoats. By looking at MEK double rubs results, it is apparent tothose skilled in the art that neutralization of basecoat with acarbodiimide (ADDITIVE A) or an epoxy (ADDITIVE B) improves chemicalresistance of clear-coat significantly. Examples D, E, F, and G hadsignificantly higher MEK double rubs than their respective negativecontrols of Examples B, and C. In addition, Examples D, E, F, and G hadvery similar MEK double rubs in comparison to positive control ExampleA.

TABLE I Ex. A Ex. B Ex. C Ex. D Ex. E Ex. F Ex. G BASECOAT BASECOAT A(mL) — 100 — 100 100 — — BASECOAT B (mL) — — 100 — — 100 100 ADDITIVE A— — — 3 — 3 — ADDITIVE B — — — — 3 — 3 REDUCER A (mL) — 50 50 50 50 5050 CLEAR-COAT POLYOL A 9.13 9.13 9.13 9.13 9.13 9.13 9.13 ADDITIVE A0.39 0.39 0.39 0.39 0.39 0.39 0.39 ADDITIVE C 0.38 0.38 0.38 0.38 0.380.38 0.38 CATALYST A 0.20 0.20 0.20 0.20 0.20 0.20 0.20 n-BA 25.17 25.1725.17 25.17 25.17 25.17 25.17 URETDIONE A 64.74 64.74 64.74 64.74 64.7464.74 64.74 MEK Double Rubs 1 Day 85 15 30 45 70 40 80 1 Week 450 95 350380 420 450 450

This specification has been written with reference to variousnon-limiting and non-exhaustive embodiments. However, it will berecognized by persons having ordinary skill in the art that varioussubstitutions, modifications, or combinations of any of the disclosedembodiments (or portions thereof) may be made within the scope of thisspecification. Thus, it is contemplated and understood that thisspecification supports additional embodiments not expressly set forthherein. Such embodiments may be obtained, for example, by combining,modifying, or reorganizing any of the disclosed steps, components,elements, features, aspects, characteristics, limitations, and the like,of the various non-limiting embodiments described in this specification.In this manner, Applicants reserve the right to amend the claims duringprosecution to add features as variously described in thisspecification, and such amendments comply with the requirements of 35U.S.C. § 112(a), and 35 U.S.C. § 132(a).

Various aspects of the subject matter described herein are set out inthe following numbered clauses:

1. A system comprising: an allophanate composition and one of aneutralized basecoat, wherein the allophanate composition comprises aneutralized polyol, a polyuretdione resin, a tertiary amine catalyst, anadditive package, and a reducer, and wherein the neutralized basecoatcomprises an acid scavenger and a pigment.

2. The system according to clause 1, wherein the tertiary amine is anamidine.

3. The system according to clause 1, wherein the tertiary amine isselected from the group consisting of one selected from the groupconsisting of 1,8-diazabicyclo[5.4.0]undec-7-ene,7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,1,4,5,6-tetrahydro-1,2-dimethylpyrimidine, 1,2,4-triazole, sodiumderivative and 2-tert-butyl-1,1,3,3-tetramethylguanidine, andcombinations thereof.

4. The system according to clause 1, wherein the neutralized polyolcomprises the reaction product of a polyol and an acid scavengerselected from the group consisting of carbodiimides and epoxies.

5. The system according to clause 4, wherein the polyol is selected fromthe group consisting of polyalkylene ether polyols, polyester polyolshydroxyl containing polycaprolactones, hydroxyl-containing (meth)acrylicpolymers, polycarbonate polyols, polyurethane polyols, and combinationsthereof.

6. The system according to one of clauses 1 to 5, wherein theneutralized basecoat comprises the reaction product of a basecoat withan acid scavenger selected from the group consisting of carbodiimidesand epoxies.

7. The system according to one of clauses 1 to 6, wherein the pigment isselected from the group consisting of inorganic white pigments,inorganic chromatic pigments, iron oxide pigments, oxidic mixed-phasepigments, organic pigments, and inorganic black pigments.

8. The system according to one of clauses 1 to 7, wherein the pigment isselected from the group consisting of titanium dioxide, zinc oxide(ZnO), zirconium oxide, lead white, lead sulfate, zinc sulfide, andlithopones, titanium dioxide, bismuth vanadate, cadmium, cerium sulfide,chromate, ultramarine iron blue pigments, Color Index Pigment Yellow 42,Pigment Red 101, Pigment Blue 11, Pigment Brown 6, transparent ironoxide pigments, Color Index Pigment Green 17, Pigment Green 18, nickeltitanium yellow, chromium titanium yellow, cobalt green, cobalt blue,zinc iron brown, chromium iron brown, iron manganese black, spinelblack, carbon black, and black iron oxide.

9. The system according to one of clauses 1 to 8, wherein the systemfurther includes an additive package selected from the group consistingof flow control additives, wetting agents, pigments (colorants), andsolvents.

10. The system according to one of clauses 1 to 9, wherein thepolyuretdione resin comprises the reaction product of catalyticdimerization of an isocyanate.

11. The system according to clause 10, wherein the isocyanate isselected from the group consisting of 1,4-tetramethylene diisocyanate,1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylenediisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and1,4-diisocyanate, 1-isocyanato-2-isocyanato-methyl cyclopentane,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane (isophoronediisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 1,3- and1,4-bis(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,α,α,α′,α′-tetramethyl-1,3- and 1,4-xylene diisocyanate,1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, and 2,4- and2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI),diphenylmethane diisocyanate (MDI), pentane diisocyanate(PDI)—bio-based, and, isomers of any of these.

12. The system according to one of clauses 1 to 11, wherein the reduceris selected from the group consisting of n-butyl acetate, ethyl acetate,2-methoxy-1-methylethyl acetate, 1-methoxy-2-propyl acetate,2-methoxy-1-propyl acetate, 2-ethoxyethyl acetate, n-heptane,methylcyclohexane, toluene, acetone, VM&P naphtha, naphtha, lightaliphatic solvent naphtha, acetate, isobutyl acetate, mixed xylenes,ethylbenzene, methyl ethyl ketone, dimethyl ketone, methyl n-amylketone, methyl isobutyl ketone, 1,2,4 trimethyl benzene,isopropylbenzene, ethyl benzene, 1-chloro-4 (triflouromethyl) benzene,propylene glycol methyl ether, and ethyl-3-ethoxy propionate andcombinations thereof.

13. One of a coating, an adhesive, a casting, a composite, and a sealantcomprising the system made according to one of clauses 1 to 12.

14. A method of applying the system according to one of clauses 1 to 13to a substrate, wherein the method comprises at least one of spraying,dipping, flow coating, rolling, brushing, and pouring.

15. A method of making an allophanate system comprising: combining aneutralized polyol with a polyuretdione resin in the presence of atertiary amine catalyst, an additive package, and a reducer to producean allophanate composition, and contacting the allophanate compositionwith a neutralized basecoat comprising an acid scavenger and a pigment.

16. The method according to clause 15 wherein the tertiary aminecatalyst comprises an amidine.

17. The method according to clause 15, wherein the tertiary amine isselected from the group consisting of one selected from the groupconsisting of 1,8-diazabicyclo[5.4.0]undec-7-ene,7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,1,4,5,6-tetrahydro-1,2-dimethylpyrimidine, 1,2,4-triazole, sodiumderivative and 2-tert-butyl-1,1,3,3-tetramethyl-guanidine, andcombinations thereof.

18. The method according to one of clauses 15 to 17, wherein theneutralized polyol comprises the reaction product of a polyol and anacid scavenger selected from the group consisting of carbodiimides andepoxies.

19. The method according to clause 18, wherein the polyol is selectedfrom the group consisting of polyalkylene ether polyols, polyesterpolyols, hydroxyl containing polycaprolactones, hydroxyl-containing(meth)acrylic polymers, polycarbonate polyols, polyurethane polyols, andcombinations thereof.

20. The method according to one of clauses 15 to 19, wherein neutralizedbasecoat comprises the reaction product of a basecoat and an acidscavenger selected from the group consisting of carbodiimides andepoxies.

21. The method according to one of clauses 15 to 20, wherein the pigmentis selected from the group consisting of inorganic white pigments,inorganic chromatic pigments, iron oxide pigments, oxidic mixed-phasepigments, organic pigments, and inorganic black pigments.

22. The method according to one of clauses 15 to 21, wherein the pigmentis selected from the group consisting of titanium dioxide, zinc oxide(ZnO), zirconium oxide, lead white, lead sulfate, zinc sulfide, andlithopones, titanium dioxide, bismuth vanadate, cadmium, cerium sulfide,chromate, ultramarine iron blue pigments, Color Index Pigment Yellow 42,Pigment Red 101, Pigment Blue 11, Pigment Brown 6, transparent ironoxide pigments, Color Index Pigment Green 17, Pigment Green 18, nickeltitanium yellow, chromium titanium yellow, cobalt green, cobalt blue,zinc iron brown, chromium iron brown, iron manganese black, spinelblack, carbon black, and black iron oxide.

23. The method according to one of clauses 15 to 22, further includingan additive package selected from the group consisting of flow controladditives, wetting agents, pigments (colorants), and solvents.

24. The method according to one of clauses 15 to 23, wherein thepolyuretdione resin comprises the reaction product of catalyticdimerization of an isocyanate.

25. The method according to clause 24, wherein the isocyanate isselected from the group consisting of 1,4-tetramethylene diisocyanate,1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylenediisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and1,4-diisocyanate, 1-isocyanato-2-isocyanato-methyl cyclopentane,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane (isophoronediisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 1,3- and1,4-bis(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,α,α,α′,α′-tetramethyl-1,3- and 1,4-xylene diisocyanate,1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, and 2,4- and2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI),diphenylmethane diisocyanate (MDI), pentane diisocyanate(PDI)—bio-based, and, isomers of any of these.

26. The method according to one of clauses 15 to 25, wherein the reduceris selected from the group consisting of n-butyl acetate, ethyl acetate,2-methoxy-1-methylethyl acetate, 1-methoxy-2-propyl acetate,2-methoxy-1-propyl acetate, 2-ethoxyethyl acetate, n-heptane,methylcyclohexane, toluene, acetone, VM&P naphtha, naphtha, lightaliphatic solvent naphtha, acetate, isobutyl acetate, mixed xylenes,ethylbenzene, methyl ethyl ketone, dimethyl ketone, methyl n-amylketone, methyl isobutyl ketone, 1,2,4 trimethyl benzene,isopropylbenzene, ethyl benzene, 1-chloro-4 (triflouromethyl) benzene,propylene glycol methyl ether, and ethyl-3-ethoxy propionate andcombinations thereof.

27. One of a coating, an adhesive, a casting, a composite, and a sealantcomprising the allophanate system made according to one of clauses 15 to26.

28. A method of applying the allophanate system made according to one ofclauses 15 to 27 to a substrate, wherein the method comprises at leastone of spraying, dipping, flow coating, rolling, brushing, and pouring.

What is claimed is:
 1. A system comprising: an allophanate compositioncomprising a neutralized polyol, a polyuretdione resin, a tertiary aminecatalyst, an additive package, and a reducer; and a neutralized basecoatcomprising an acid scavenger and a pigment.
 2. The system according toclaim 1, wherein the tertiary amine is an amidine.
 3. The systemaccording to claim 1, wherein the tertiary amine is selected from thegroup consisting of one selected from the group consisting of1,8-diazabicyclo[5.4.0]undec-7-ene,7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,1,4,5,6-tetrahydro-1,2-dimethylpyrimidine, 1,2,4-triazole, sodiumderivative and 2-tert-butyl-1,1,3,3-tetramethylguanidine, andcombinations thereof.
 4. The system according to claim 1, wherein theneutralized polyol comprises the reaction product of a polyol and anacid scavenger selected from the group consisting of carbodiimides andepoxies.
 5. The system according to claim 4, wherein the polyol isselected from the group consisting of polyalkylene ether polyols,polyester polyols hydroxyl containing polycaprolactones,hydroxyl-containing (meth)acrylic polymers, polycarbonate polyols,polyurethane polyols, and combinations thereof.
 6. The system accordingto claim 1, wherein the neutralized basecoat comprises the reactionproduct of the basecoat with an acid scavenger selected from the groupconsisting of carbodiimides and epoxies.
 7. The system according toclaim 1, wherein the pigment is selected from the group consisting ofinorganic white pigments, inorganic chromatic pigments, iron oxidepigments, oxidic mixed-phase pigments, organic pigments, and inorganicblack pigments.
 8. The system according to claim 1, wherein the pigmentis selected from the group consisting of titanium dioxide, zinc oxide(ZnO), zirconium oxide, lead white, lead sulfate, zinc sulfide, andlithopones, titanium dioxide, bismuth vanadate, cadmium, cerium sulfide,chromate, ultramarine iron blue pigments, Color Index Pigment Yellow 42,Pigment Red 101, Pigment Blue 11, Pigment Brown 6, transparent ironoxide pigments, Color Index Pigment Green 17, Pigment Green 18, nickeltitanium yellow, chromium titanium yellow, cobalt green, cobalt blue,zinc iron brown, chromium iron brown, iron manganese black, spinelblack, carbon black, and black iron oxide.
 9. The system according toclaim 1, wherein the system further includes an additive packageselected from the group consisting of flow control additives, wettingagents, pigments (colorants), and solvents.
 10. The system according toclaim 1, wherein the polyuretdione resin comprises the reaction productof catalytic dimerization of an isocyanate.
 11. The system according toclaim 10, wherein the isocyanate is selected from the group consistingof 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate,2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylenediisocyanate, cyclohexane-1,3- and 1,4-diisocyanate,1-isocyanato-2-isocyanato-methyl cyclopentane,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane (isophoronediisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 1,3- and1,4-bis(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,α,α,α′,α′-tetramethyl-1,3- and 1,4-xylene diisocyanate,1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, and 2,4- and2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI),diphenylmethane diisocyanate (MDI), pentane diisocyanate(PDI)—bio-based, and, isomers of any of these.
 12. The system accordingto claim 1, wherein the reducer is selected from the group consisting ofn-butyl acetate, ethyl acetate, 2-methoxy-1-methylethyl acetate,1-methoxy-2-propyl acetate, 2-methoxy-1-propyl acetate, 2-ethoxyethylacetate, n-heptane, methylcyclohexane, toluene, acetone, VM&P naphtha,naphtha, light aliphatic solvent naphtha, acetate, isobutyl acetate,mixed xylenes, ethylbenzene, methyl ethyl ketone, dimethyl ketone,methyl n-amyl ketone, methyl isobutyl ketone, 1,2,4 trimethyl benzene,isopropylbenzene, ethyl benzene, 1-chloro-4 (triflouromethyl) benzene,propylene glycol methyl ether, and ethyl-3-ethoxy propionate andcombinations thereof.
 13. One of a coating, an adhesive, a casting, acomposite, and a sealant comprising the system made according toclaim
 1. 14. A method of applying the system according to claim 1 to asubstrate, wherein the method comprises at least one of spraying,dipping, flow coating, rolling, brushing, and pouring.
 15. A method ofmaking an allophanate system comprising: combining a neutralized polyolwith a polyuretdione resin in the presence of a reducer, a tertiaryamine catalyst, and an additive package, to produce an allophanatecomposition; and contacting the allophanate composition with aneutralized basecoat comprising an acid scavenger and a pigment.
 16. Themethod according to claim 15 wherein the tertiary amine catalystcomprises an amidine.
 17. The method according to claim 15, wherein thetertiary amine is selected from the group consisting of one selectedfrom the group consisting of 1,8-diazabicyclo[5.4.0]undec-7-ene,7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,1,4,5,6-tetrahydro-1,2-dimethylpyrimidine, 1,2,4-triazole, sodiumderivative and 2-tert-butyl-1,1,3,3-tetramethylguanidine, andcombinations thereof.
 18. The method according to claim 15, wherein theneutralized polyol comprises the reaction product of a polyol and anacid scavenger selected from the group consisting of carbodiimides andepoxies.
 19. The method according to claim 18, wherein the polyol isselected from the group consisting of polyalkylene ether polyols,polyester polyols, hydroxyl containing polycaprolactones,hydroxyl-containing (meth)acrylic polymers, polycarbonate polyols,polyurethane polyols, and combinations thereof.
 20. The allophanatesystem according to claim 15, wherein neutralized basecoat comprises thereaction product of a basecoat and an acid scavenger selected from thegroup consisting of carbodiimides and epoxies.
 21. The method accordingto claim 15, wherein the pigment is selected from the group consistingof inorganic white pigments, inorganic chromatic pigments, iron oxidepigments, oxidic mixed-phase pigments, organic pigments, and inorganicblack pigments.
 22. The method according to claim 15, wherein thepigment is selected from the group consisting of titanium dioxide, zincoxide (ZnO), zirconium oxide, lead white, lead sulfate, zinc sulfide,and lithopones, titanium dioxide, bismuth vanadate, cadmium, ceriumsulfide, chromate, ultramarine iron blue pigments, Color Index PigmentYellow 42, Pigment Red 101, Pigment Blue 11, Pigment Brown 6,transparent iron oxide pigments, Color Index Pigment Green 17, PigmentGreen 18, nickel titanium yellow, chromium titanium yellow, cobaltgreen, cobalt blue, zinc iron brown, chromium iron brown, iron manganeseblack, spinel black, carbon black, and black iron oxide.
 23. The methodaccording to claim 15, further including an additive package selectedfrom the group consisting of flow control additives, wetting agents, andpigments (colorants), solvents.
 24. The method according to claim 15,wherein the polyuretdione resin comprises the reaction product ofcatalytic dimerization of an isocyanate.
 25. The method according toclaim 24, wherein the isocyanate is selected from the group consistingof 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate,2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylenediisocyanate, cyclohexane-1,3- and 1,4-diisocyanate,1-isocyanato-2-isocyanato-methyl cyclopentane,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane (isophoronediisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 1,3- and1,4-bis(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,α,α,α′,α′-tetramethyl-1,3- and 1,4-xylene diisocyanate,1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, and 2,4- and2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI),diphenylmethane diisocyanate (MDI), pentane diisocyanate(PDI)—bio-based, and, isomers of any of these.
 26. The method accordingto claim 15, wherein the reducer is selected from the group consistingof n-butyl acetate, ethyl acetate, 2-methoxy-1-methylethyl acetate,1-methoxy-2-propyl acetate, 2-methoxy-1-propyl acetate, 2-ethoxyethylacetate, n-heptane, methylcyclohexane, toluene, acetone, VM&P naphtha,naphtha, light aliphatic solvent naphtha, acetate, isobutyl acetate,mixed xylenes, ethylbenzene, methyl ethyl ketone, dimethyl ketone,methyl n-amyl ketone, methyl isobutyl ketone, 1,2,4 trimethyl benzene,isopropylbenzene, ethyl benzene, 1-chloro-4 (triflouromethyl) benzene,propylene glycol methyl ether, and ethyl-3-ethoxy propionate andcombinations thereof.
 27. One of a coating, an adhesive, a casting, acomposite, and a sealant comprising the allophanate system madeaccording to claim
 15. 28. A method of applying the allophanate systemmade according claim 15 to a substrate, wherein the method comprises atleast one of spraying, dipping, flow coating, rolling, brushing, andpouring.